Enhanced energy storage properties of Bi(Ni2/3Nb1/6Ta1/6)O3–NaNbO3 solid solution lead-free ceramics

Sodium niobate energy storage ceramics with good environmental performance are widely used in electric power conversion and pulse power system, large energy storage density and high efficiency, huge power density and charge and discharge faster. In this work, (1-x)NaNbO₃-xBi(Ni_2/3Nb_1/6Ta_1/6)O₃ [(1-x)NN-xBNNT] (0.12 ≤ x ≤ 0.18) ceramics system were prepared by solid state reaction method. By introducing Bi(Ni_2/3Nb_1/6Ta_1/6)O₃ (BNNT), a relaxation strategy was constructed, which significantly improved the energy storage properties of NaNbO₃ (NN) based ceramics. Finally, comparatively high recoverable energy density (W_rec) of 3.43 J/cm³ and large energy storage efficiency (η) of 83.3% were obtained in 0.86NN-0.14BNNT ceramics. Besides discharge energy density (W_d) of 0.69 J/cm³, ultra fast charge-discharge rate (t_0.9) of 55 ns, the power density (P_D) of 70.66 MW/cm³ and the current density (C_D) of 883.23 A/cm² were also observed in ceramic.     

Realizing high energy density and superior charge-discharge characteristics in NN-10BT-based ceramics

The low recoverable energy storage density (W_rec) of bulk ceramics has long limited their miniaturization and lightweight development. Here, we designed the (1-x)(0.90NaNbO₃-0.10BaTiO₃)-xNa_0.2Bi_0.4La_0.2TiO₃ (NN-10BT-xNBLT) ceramics. With the introduction of NBLT, the dielectric breakdown strength (BDS) of NN-10BT-based ceramics increased from 174.8 kV/cm to 289.1 kV/cm. A promising finding is that the NN-10BT-15NBLT ceramic has an ultrahigh energy storage density W of 3.42 J/cm³ and a large energy storage efficiency η of 78.9%, as well as excellent frequency and thermal stability. The NN-10BT-15NBLT ceramic, on the other hand, has an outstanding current density C_D of 1021.21 A/cm² together with a high power density P_D of 102.12 MW/cm³ at 200 kV/cm. Most importantly, the variation of charge-discharge properties (C_D and P_D) is only ?7.8% after 10⁴ cycles, suggesting that the capacitor has potential practical application significance.     

Highly-reliable dielectric capacitors with excellent comprehensive energy-storage properties using Bi0.5Na0.5TiO3-based relaxor ferroelectric ceramics

The development of capacitors with high reliability and good comprehensive performances is of great significance for practical applications. In this work, lead-free relaxor ferroelectric (FE) ceramics of (1-x)(0.5(Bi_0.5Na_0.5)TiO₃-0.5SrTiO₃)-xBi(Mg_2/3Nb_1/3)O₃ ((1-x)(BNT-ST)-xBMN) were prepared by a conventional solid-state reaction method. The introduction of BMN was found to enhance local structure disorder, leading to the significantly reduced size of FE nanodomains, which is responsible for the slim polarization-electric field hysteresis loops. A giant energy-storage density of 6.62 J/cm³ and a high efficiency of 82 % can be achieved simultaneously under a moderate electric field of 34 kV/mm at x = 0.08. It also exhibits high discharge density ～ 2.74 J/cm³, large power density ～ 248 MW/cm³ and ultrafast discharge rate ～ 28 ns at 20 kV/mm in addition to excellent temperature (10–130 °C) and frequency (1–100 Hz) stabilities. These results demonstrate that the (1-x)(BNT-ST)-xBMN ceramic system is a promising lead-free candidate for advanced pulsed power capacitor applications.     

(1-x)Bi0.5Na0.47Li0.03TiO3-xNaNbO3 lead-free ceramics with superior energy storage performances and good temperature stability

Dielectric capacitors show great potential in superior energy storage devices. However, the energy density of these capacitors is still inadequate to meet the requirement of energy storage applications. In this study, the Bi_0.5Na_0.47Li_0.03TiO₃-xNaNbO₃ (BNLT-xNN) ceramics were prepared via conventional solid-phase reaction. Results showed that NN can efficaciously enhance the breakdown strength (E_b) and the relaxation behavior of the BNLT ceramic because of the broken ferroelectric long-range order. When x = 0.3, the maximum E_b reached 350 kV/cm, at which the 0.7BNLT-0.3NN ceramic exhibited the high recoverable energy storage density (W_rec) of 4.83 J/cm³ and great efficiency (η) of 78.9%. The ceramic demonstrated good temperature stability at 20 °C-160 °C and excellent fatigue resistance. Additionally, the 0.7BNLT-0.3NN ceramic presented high power density (P_D; ～77.58 MW/cm³), large current density (C_D; ～861.99 A/cm²), and quite short discharge time (t_0.9; ～0.090 μs). These results indicated that the 0.7BNLT-0.3NN material has excellent energy storage properties and various application prospects.     

Large energy density with excellent stability in fine-grained (Bi0.5Na0.5)TiO3-based lead-free ceramics

In this work, fine-grained (0.95-x)(Bi_0.5Na_0.5)TiO₃-0.05BaTiO₃-xBi(Zn_2/3Nb_1/3)O₃ (abbreviated as BNT-BT-xBZN, x = 0～0.20) lead-free ceramics are successfully prepared, showing a high energy storage performance. The addition of BZN results in decreased grain size, enhanced breakdown strength and stronger relaxor behavior with polar nanoregions. Slimmer P-E loops are thereby achieved, leading to the improvement of energy density and efficiency. As a result, a high W_D of ～2.83 J/cm³ is achieved under a relatively low electric field of 18 kV/mm in the x = 0.125 ceramic with submicron-sized grains (～0.4 μm). The W_D value is larger than that of x = 0 ceramic by ～800%. Furthermore, the x = 0.125 ceramic possesses excellent frequency stability and strong fatigue endurance. The BNT-BT-xBZN lead-free ceramics show promising potential for application in high energy density ceramic capacitors.     

Ultra-fast charge-discharge and high energy storage density realized in NaNbO3–La(Mn0.5Ni0.5)O3 ceramics

Lead-free antiferroelectric (AFE) NaNbO₃ (NN) is one of promising materials for dielectric capacitors, but the recoverable energy-storage density and efficiency get restrained owing to huge remanent polarization and limited dielectric breakdown field strength. In this work, a variety of NN based lead-free bulk (1-x)NaNbO₃-xLa(Mn_0.5Ni_0.5)O₃ (abbreviated as (1-x)NN-xLMN, x = 0, 0.05, 0.10, 0.15, 0.20) ceramics were designed using a solid-state synthesis method. Remarkably, an ultra-fast charge-discharge speed 47 ns and an acceptable recoverable energy-storage density W_rec ~1.77 J/cm³ with a high efficiency η = 77% were obtained under the E_b of 200 kV/cm at x = 0.05. The superior energy storage performance is attributed to the regulation of domain size and voltage resistance by special ions substitution of A and B sites. This work not only proposes an efficient strategy to realize high recoverable energy-storage density and efficiency, but also provide an candidate material for application of advanced pulsed power capacitors.     

Excellent energy-storage properties of NaNbO3-based lead-free antiferroelectric orthorhombic P-phase (Pbma) ceramics with repeatable double polarization-field loops

The energy-storage performance of stable NaNbO₃-based antiferroelectric (AFE) ceramics was for the first time reported in (0.94-x)NaNbO₃-0.06BaZrO₃-xCaZrO₃ lead-free ceramics. A gradual evolution from an instable AFE phase (x≤0.01) to an orthorhombic AFE P phase (Pbma) (0.01<x≤0.05) was found to accompany the appearance of repeatable double-like polarization versus electric field loops although poled samples (x<0.01) own an AFE monoclinic phase (P2₁). Interestingly, compared with x≤0.01 samples with instable antiferroelectricity, a relatively high recoverable energy storage density W_rec ? 1.59 J/cm³ (@ 0.1 Hz) and a storage efficiency η of ?30% were achieved in the x = 0.04 ceramic. Moreover, a high W_rec of > 1.16 J/cm³ and an outstanding charge-discharge performance with fast discharge rate (t_0.9 < 100 ns) were generated in the temperature range from room temperature to 180 °C in the x = 0.04 ceramic. These results suggest that NaNbO₃-based AFE P-phase ceramics could be new potential dielectric materials for high-energy storage capacitors.     

Enhanced energy-storage properties of (1-x)(0.7Bi0.5Na0.5TiO3-0.3Bi0.2Sr0.7TiO3)-xNaNbO3 lead-free ceramics

A series of (1-x)(0.7Bi_0.5Na_0.5TiO₃-0.3Bi_0.2Sr_0.7TiO₃)-xNaNbO₃ (BNT-BST-100xNN) lead-free ceramics were fabricated using conventional solid-state reaction technique. The phase behavior, microstructure, dielectric, ac impedance and energy-storage properties of the sintered ceramics were systematically investigated. XRD patterns and surface SEM micrographs revealed the introduction of NaNbO₃ didn't change the perovskite structure of BNT-BST at low doping level. The NaNbO₃ doping gave rise to slimmer P-E loops and thus gained enhanced energy storage properties. Therefore, a maximum energy storage density of 1.03 J/cm³ was achieved at 85 kV/cm at x = 0.01 via increasing the dielectric breakdown strength (DBS). Temperature-dependent dielectric permittivity illustrated the enhanced relaxor characteristics, implying the long-rang ferroelectric order was further damaged due to the introduction of NaNbO₃. The results above indicate the sintered ternary ceramics can be a promising lead-free candidate for energy storage capacitors.     

NaNbO3-based short-range antiferroelectric ceramics with ultrahigh energy storage performance

Lead-free NaNbO₃ (NN) antiferroelectric ceramics provide superior energy storage performance and good temperature/frequency stability, which are solid candidates for dielectric capacitors in high power/pulse electronic power systems. However, their conversion of the antiferroelectric P phase to the ferroelectric Q phase at room temperature is always accompanied with large remnant polarization (P_r), which significantly reduces their effective energy storage density and efficiency. In this study, to optimize the energy storage properties, short-range antiferroelectric (0.95-x)NaNbO₃-xBi(Mg_2/3Nb_1/3)O₃-0.05CaZrO₃ (xBMN) ceramics were designed to stabilize the antiferroelectric phase, in which the local random fields were simultaneously constructed. The results showed that the antiferroelectric orthorhombic P phase was transformed into the R phase, and the local short-range random fields were generated, which effectively inhibited the hysteresis loss and P_r. Of great interest is that the 0.12BMN ceramics displayed a large recoverable energy storage density (W_rec) of 5.9 J/cm³ and high efficiency (η) of 85% at the breakdown strength (E_b) of 640 kV/cm. The material also showed good frequency stability in the frequency range of 2–300 Hz, excellent temperature stability in the temperature range of 20–110 ℃, and a very short discharge time (t_0.9∼4.92 μs). These results indicate that xBMN ceramics have great potential for advanced energy storage capacitor applications.     

Simultaneously enhanced energy storage density and efficiency in novel BiFeO3-based lead-free ceramic capacitors

In this work, a series of novel lead-free (1-x)Bi_0.83Sm_0.17Fe_0.95Sc_0.05O₃-x(0.85BaTiO₃-0.15Bi(Mg_0.5Zr_0.5)O₃) [(1-x)BSFS-x(BT-BMZ), x = 0.45?0.85] relaxor ceramics were prepared by solid phase sintering, and their dielectric properties and energy storage performances were explored. It was revealed that all the samples have a dense structure with pure pseudo-cubic phase. With the increase of x, the ferroelectric hysteresis loop is gradually slimmed accompanied by a decreasing polarization, indicating an enhanced relaxor behavior. Moreover, the electric breakdown strength increases linearly with x due to the fine grain size and enhanced relative density. Interestingly, a large recoverable energy density (～3.2 J/cm³) with an outstanding efficiency (～92 %) is achieved under an electric field ～206 kV/cm for the optimized component x = 0.75, which is superior to other reported lead-free ceramic systems. Moreover, the optimized ceramics of 0.25BSFS-0.75(BT-BMZ) show good thermal stability (25?100 °C) and excellent fatigue endurance (cycle number: > 10⁵) in energy storage performances. This work opens up a new route to tailor lead-free dielectric ceramics with high energy storage properties.     

Designing novel lead-free NaNbO3-based ceramic with superior comprehensive energy storage and discharge properties for dielectric capacitor applications via relaxor strategy

There are urgent demands for high performance capacitors with superior energy storage density and discharge performances. In this work, novel NaNbO₃-based lead-free ceramics (0.91NaNbO₃-0.09Bi(Zn_0.5Ti_0.5)O₃) with high energy storage capability, high power density and fast discharge speed were designed and prepared. Bi(Zn_0.5Ti_0.5)O₃ was chosen for the purpose to reduce the remnant polarization and improve the induced polarization. Consequently, a large stored energy storage density (W_s˜ 3.51 J/cm³) and high recoverable energy storage density (W_rec˜ 2.20 J/cm³) were obtained in 0.91NaNbO₃-0.09Bi(Zn_0.5Ti_0.5)O₃ ceramic under a high breakdown strength of 250 kV/cm, with excellent thermal stability in the range of 20–120 °C. More importantly, the investigated ceramics exhibited high power density (P_D˜ 20 MW/cm³) and ultrafast discharge rate (t_0.9˜ 0.25 μs), demonstrating potential application in pulse powehr systems. This work provides an effective means of achieving excellent energy storage and discharge performances in NaNbO₃-based ceramics for application in dielectric capacitors.     

Enhanced energy storage performance in Na(1-3x)BixNb0.85Ta0.15O3 relaxor ferroelectric ceramics

High-performance lead-free dielectric containers have excellent energy storage performance such as higher power density and energy density. While being eco-friendly materials, lead-free dielectric materials are more suitable for pulse power systems than other dielectric materials. In this study, Ta⁵⁺and Bi³⁺ ions were introduced into the A site and B site of the NaNbO₃ matrix. The introduction of Bi³⁺ ions induced the formation of a vacancy in the A site, yielding Na_(1-3x)Bi_xNb_0.85Ta_0.15O₃ (NBNT, x = 0.05, 0.08, 0.11, 0.14) ceramics. The recoverable energy density (W_rec) and the energy storage efficiency (η) were highest for the Na_0.67Bi_0.11Nb_0.85Ta_0.15O₃ ceramic, with values of 3.37 J/cm³ and 89% respectively. Batteries employing the Na_0.67Bi_0.11Nb_0.85Ta_0.15O₃ ceramic achieved a current density of 830.4 A/cm², an energy density of 49.8 MW/cm³ and 60.2 ns discharge time. These results show that the Na_0.67Bi_0.11Nb_0.85Ta_0.15O₃ ceramic is an effective energy storage material with broad application prospects.     

Achieving high energy storage performance below 200 kV/cm in BaTiO3-based medium-entropy ceramics

A small applied electric field is particularly crucial in the practical application of dielectric ceramic capacitors, since it means a longer lifetime of the capacitors in practical energy storage applications. Based on the traditional ferroelectric BaTiO₃, the (1-x)(Ba_0.6Na_0.2Bi_0.2)TiO₃-xNaNbO₃ medium-entropy material is designed in this paper, which correlates configuration entropy with energy storage performance. The findings demonstrate that the BNBT-0.15NN ceramic synchronously achieves high energy storage density (2.95 J/cm³) and the energy storage efficiency (95.2%) at 180 kV/cm when the configuration entropy rises to 1.43R. The idea of medium-entropy energy storage under low electric field is proposed for the first time, opening up a new avenue for research into the preparation of high energy storage dielectric ceramics via exploring medium-entropy composition.     

0.74NaNbO3–0.26Sr(Mg1/3Nb2/3)O3 lead-free dielectric ceramics with high energy storage properties

Sodium niobate (NaNbO₃) ceramics are commonly investigated for use as energy storage ceramics because of their excellent properties. NaNbO₃ ceramics are modified mainly by doping with a Bi-based composite perovskite, that is, by the nonequivalent doping of Bi³⁺ at the A site of the NaNbO₃ ceramic. In addition, the high volatility of Bi at high temperatures increases the defects in the ceramics. This paper provides a new idea of doping modification of sodium NaNbO₃-based energy storage ceramics. Here, (1?x)NaNbO₃–xSr(Mg_1/3Nb_2/3)O₃ (x = 0.17, 0.20, 0.23, 0.26) ceramics were prepared by doping NaNbO₃ with an Sr-based composite perovskite. Compared with Bi-based composite perovskite, Sr-based composite perovskite doping of NaNbO₃ ceramics can also obtained good energy storage properties: a total energy storage density of 4.28 J/cm³ and an energy storage efficiency of 89.3%. In addition, the ceramics exhibited good frequency stability (2–200 Hz) and a high charge/discharge rate (1.06 μs).     

Piezoelectric properties of (1-x)BZT-xBCT system for energy harvesting applications

In this study, we investigated (1-x)Ba(Zr_0.2Ti_0.8)O₃–x(Ba_0.7Ca_0.3)TiO₃ lead-free piezoelectric ceramics for energy harvester applications. The (1-x)BZT-xBCT ceramic is a promising lead-free piezoelectric material in the field of piezoelectric energy harvesting. Piezoelectric and energy properties of (1-x)BZT-xBCT ceramics were analyzed to confirm the possibility of using them as energy-harvesting materials. Especially, the vicinity of the phase convergence region was investigated to improve their piezoelectric properties. In the phase convergence region, cubic, rhombohedral, orthorhombic, and tetragonal regions co-exist within the narrow region. Near the phase transition region between the orthorhombic and tetragonal phase, the highest piezoelectric property d₃₃?=?464 pC/N and the highest energy density of 158.5 μJ/cm³ were observed. This output energy density of 158.5 μJ/cm³ is the recorded highest value among lead-free ceramics. We found that the optimal sintering temperature was 1475?°C and the optimal composition was BZT-0.5BCT.     

Realizing high comprehensive energy storage performances of BNT-based ceramics for application in pulse power capacitors

Lead-free ceramic capacitors play an important role in electrical energy storage devices because of their ultrafast charge/discharge rates and high power density. However, simultaneously obtaining large energy storage capability, high efficiency and superior temperature stability has been a huge challenge for practical applications of ceramic capacitors. Here, the relaxor ferroelectric (1-x)[0.8Bi_0.5Na_0.5TiO₃-0.2Ba(Zr_0.3Ti_0.7)O₃]-xSr_0.7La_0.2TiO₃ ((1-x)(BNT-BZT)-xSLT) ceramics are prepared through solid-state reaction method to obtain excellent comprehensive energy storage performances. Particularly, high recoverable energy density (W_rec ～ 2.6 J/cm³) as well as superior efficiency (η ～ 92.2 %) can be achieved simultaneously under 210 kV/cm with composition of x = 0.3. Meanwhile, the corresponding ceramic shows excellent temperature (20?140 °C), frequency (1?200 Hz) and cycle stabilities (10⁶ st). Additionally, the 0.7(BNT-BZT)-0.3SLT ceramic also displays high power density (P_D ～ 38.8 MW/cm³) and extremely short discharge time (τ_0.9 ～ 0.11 μs). Therefore, this study provides a useful guideline for designing novel BNT-based ceramics with superior comprehensive energy storage performances.     

A new family of sodium niobate-based dielectrics for electrical energy storage applications

Although tremendous achievements have been made in enhancing recoverable energy storage density (W_rec) of lead-free dielectric ceramics for electrical energy storage applications in recent years, these ceramics with high W_rec still have two disadvantages: complex chemical composition and difficult preparation process. In this work, we selected NaNbO₃ (NN)-based ceramics as base materials and used Bi₂O₃ as a sintering aid to reduce porosity and enhance dielectric breakdown strengths. Encouragingly, high W_rec, simple chemical composition and facile preparation process were simultaneously realized in 0.77NaNbO₃-0.23BaTiO₃ (0.77NN-0.23BT) ceramics. A large W_rec of 1.5 J cm^?3 at 175 kV cm^?1 and excellent thermal stability (variation of W_rec < 15% over the temperature range of 20?140 °C) were simultaneously achieved in 0.77NN-0.23BT ceramics. More importantly, this work could bring out the development of a series of NN-based ceramics for electrical energy storage in the future such as NN-ABO₃ (A = Ca and Sr; B = Ti and Zr).     

Enhanced energy storage performances of Bi(Ni1/2Sb2/3)O3 added NaNbO3 relaxor ferroelectric ceramics

In the development of dielectric ceramic materials, the requirements of miniaturization and integration are becoming increasingly prominent. How to obtain greater capacitance in a smaller volume is one of the important pursuits. In this paper, lead-free (1-x)NaNbO₃-xBi(Ni_1/2Sb_2/3)O₃(xBNS) with high recoverable energy storage density (W_rec) and relatively high energy storage efficiency(η) were prepared by a solid state sintering method. Bi(Ni_1/2Sb_2/3)O₃ was introduced into the Sodium niobate ceramics(NN)-based ceramics to reduce the sintering temperature and increase the maximum breakdown field strength (E_b). Finally, 0.15BNS achieved a high E_b of 460 kV/cm, W_rec of 3.7 J/cm³ and η of 77%. In addition, the sample maintained excellent stability in the frequency range of 1–120 Hz. And the 0.15BNS ceramics also exhibited high power density (P_D = 36.4 MW/cm³), large current density (C_D = 520.8 A/cm²) and relatively fast charge-discharge rate (t_0.9 = 1050 ns). These results demonstrate the potential application value of xBNS ceramics in energy storage capacitors.     

Energy storage properties in Bi(Mg1/2Sb2/3)O3-doped NaNbO3 lead-free ceramics

Sodium niobate energy storage ceramics with high energy density and efficiency can be used as potential candidate materials for pulse power devices. Doping modification of dielectric ceramic matrixes is an effective means to obtain high performance. The (1-x)NaNbO₃-xBi(Mg_1/2Sb_2/3)O₃ ceramics were designed in this work. And 0.85NaNbO₃-0.15Bi(Mg_1/2Sb_2/3)O₃ showed a large W_rec of 4.65 J/cm³ at an E_b of 580 kV/cm. Excellent frequency stability of W_rec (1.67–1.7 J/cm³) and η (86%–89.1%) over frequency range of 1–100Hz was observed. Further, good temperature stability of W_rec (1.5–1.71 J/cm³) and η (68%–87%) over abroad temperature range of 20–180 °C was attained successfully. In addition, excellent power density (P_D = 113 MW/cm³), large current density (C_D = 1255 A/cm²) and discharge speed (0.51μs) were obtained, which demonstrates the great potential practical value of this ceramic in the energy storage applications.     

Excellent energy storage performance of NaNbO3-based antiferroelectric ceramics with ultrafast charge/discharge rate

Dielectric capacitors have drawn increasing attention due to their fast charge/discharge rates and high power density. Among all known ceramic dielectric materials, antiferroelectrics are more attractive for their unique double ferroelectric hysteresis loops and higher energy densities. Here, a series of antiferroelectric ceramics x(0.95Bi_0.5Na_0.5TiO₃-0.05SrZrO₃)-(1-x)NaNbO₃ (xBNTSZ-(1-x)NN, x = 0.23, 0.30, 0.35, 0.50) have been prepared. By stabilizing the antiferroelectric phase and postponing the critical electric field of the antiferroelectric-ferroelectric phase transition, an impressive discharge energy storage density of 4.08 J/cm³ at a breakdown strength of 370 kV/cm was achieved for the 0.35BNTSZ-0.65 N N. A superior comprehensive performance for the 0.50BNTSZ-0.50 N N ceramic with a discharge energy storage density (W_dis) of 3.78 J/cm³ and an efficiency of 86 % at an electric field strength of 320 kV/cm along with excellent frequency, temperature, and fatigue stabilities (fluctuations of W_dis≤±5% within 0.01∼100 Hz, W_dis≤10 % over 20∼140 °C, and W_dis≤1% over 10⁶ cycle numbers) is realized. Furthermore, 0.50BNTSZ-0.50 N N ceramics simultaneously exhibit a high current density (622.5 A/cm²), high power density (112 MW/cm³), and fast discharge rate (t = 47 ns), all of which make it an excellent candidate for the pulsed power devices.